WO2018084320A1 - Électrode positive pour batterie au lithium-ion, et batterie au lithium-ion - Google Patents

Électrode positive pour batterie au lithium-ion, et batterie au lithium-ion Download PDF

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Publication number
WO2018084320A1
WO2018084320A1 PCT/JP2017/040164 JP2017040164W WO2018084320A1 WO 2018084320 A1 WO2018084320 A1 WO 2018084320A1 JP 2017040164 W JP2017040164 W JP 2017040164W WO 2018084320 A1 WO2018084320 A1 WO 2018084320A1
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Prior art keywords
positive electrode
active material
electrode active
group
ion battery
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PCT/JP2017/040164
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English (en)
Japanese (ja)
Inventor
南　和也
勇輔 中嶋
大澤　康彦
雄樹 草地
佐藤　一
赤間　弘
堀江　英明
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日産自動車株式会社
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Priority claimed from JP2017203993A external-priority patent/JP7058491B2/ja
Application filed by 日産自動車株式会社 filed Critical 日産自動車株式会社
Priority to MYPI2019002468A priority Critical patent/MY176071A/en
Priority to EP17867325.7A priority patent/EP3537514B1/fr
Priority to US16/346,337 priority patent/US11024835B2/en
Priority to CN201780068937.4A priority patent/CN110249456B/zh
Publication of WO2018084320A1 publication Critical patent/WO2018084320A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode for a lithium ion battery and a lithium ion battery.
  • Li 2 Mn (1-2x) Ni is used as a positive electrode active material in order to increase energy density.
  • a lithium ion battery using x Mo x O 3 (where 0 ⁇ x ⁇ 0.4) is known (see, for example, JP-A-2016-154137).
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a positive electrode for a lithium ion battery having a high energy density and capable of rapid discharge.
  • the present invention relates to a lithium battery comprising a positive electrode current collector, a positive electrode active material layer formed on the surface of the positive electrode current collector, a nonaqueous electrolyte solution containing an electrolyte containing lithium ions and a nonaqueous solvent.
  • a positive electrode for an ion battery wherein the positive electrode active material layer includes a positive electrode active material and voids, and the voids are filled with the non-aqueous electrolyte, and the battery capacity is based on the total amount of the positive electrode active material.
  • a positive electrode for a lithium ion battery wherein a ratio of a battery capacity based on a total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer is 3.5 to 15%; and
  • the present invention relates to a lithium ion battery using the battery.
  • a lithium ion battery includes a lithium ion secondary battery.
  • the present invention provides a lithium ion battery comprising a positive electrode current collector, a positive electrode active material layer formed on the surface of the positive electrode current collector, and a nonaqueous electrolyte solution containing an electrolyte containing lithium ions and a nonaqueous solvent.
  • the positive electrode active material layer includes a positive electrode active material and voids, the voids are filled with the non-aqueous electrolyte, and the battery capacity based on the total amount of the positive electrode active material is
  • the positive electrode for a lithium ion battery is characterized in that the ratio of the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer is 3.5 to 15%.
  • X to Y indicating a range includes X and Y, and means “X or more and Y or less”.
  • the diffusion distance of lithium ions is shortened, and it is considered that rapid discharge can be handled.
  • the packing density of the positive electrode active material is increased in order to increase the energy density, the amount of the non-aqueous electrolyte present around the positive electrode active material is relatively reduced, which corresponds to rapid discharge. It will be impossible.
  • the amount of the positive electrode active material is increased without increasing the packing density of the positive electrode active material, the distance between the positive electrode and the negative electrode becomes long, so that it takes time to diffuse lithium ions, and it is not possible to cope with rapid discharge. Conceivable.
  • the problem with rapid discharge is the migration rate of lithium ions from the negative electrode to the positive electrode (also called the diffusion rate) inside the lithium ion battery, but there is a sufficient amount of lithium ions around the positive electrode active material.
  • the discharge reaction when the discharge reaction is started, first, lithium ions present around the positive electrode active material are taken into the positive electrode active material.
  • discharge does not end even when lithium ions around the positive electrode active material are taken into the positive electrode active material, it is considered that lithium ions desorbed from the negative electrode are taken into the positive electrode active material and the discharge reaction proceeds.
  • the lithium ions existing around the positive electrode active material before the start of discharge can cope with the rapid discharge because the distance between the lithium ions and the positive electrode active material is very close.
  • the lithium ions present in the negative electrode in order for the lithium ions present in the negative electrode to be taken into the positive electrode, it is necessary to move between the positive electrode and the negative electrode, so that the diffusion rate of lithium ions is rate-limiting and cannot cope with rapid discharge.
  • the non-aqueous electrolyte is filled in the voids existing around the positive electrode active material, and the positive electrode active material layer with respect to the battery capacity based on the total amount of the positive electrode active material
  • the battery capacity ratio (battery capacity ratio) based on the total amount of lithium ions in the non-aqueous electrolyte present in the battery is 3.5 to 15%, so it can support rapid discharge around the positive electrode active material. It can be said that sufficient lithium ions are present.
  • the thickness of the positive electrode active material layer is increased to increase the volume ratio of the positive electrode active material layer in the entire battery, it takes time until the lithium ions supplied from the negative electrode active material are occluded in the entire positive electrode active material. Is required.
  • the battery capacity ratio has a certain value or more, it can be said that a sufficient amount of lithium ions is present around the positive electrode active material, and thus is supplied from the negative electrode active material. Instead of lithium ions, lithium ions present around the positive electrode active material are taken into the positive electrode active material, so that it is possible to cope with rapid discharge.
  • the ratio of the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer is less than 3.5%, there is sufficient lithium ion capable of supporting rapid discharge around the positive electrode active material. On the other hand, if it exceeds 15%, the rapid discharge characteristics deteriorate due to an increase in solution resistance due to the increase in the concentration of the electrolytic solution and precipitation of lithium salt.
  • the battery capacity ratio is 5 to 10%.
  • a concentration gradient of lithium ions is generated between the negative electrode and the positive electrode during discharge, and this concentration gradient also serves as a driving force for lithium ion movement, so that the discharge characteristics (rapid It is estimated that the discharge characteristics are improved.
  • the battery capacity based on the total amount of the positive electrode active material is a theoretical battery capacity based on the weight of the positive electrode active material constituting the positive electrode active material layer.
  • the theoretical value of the battery capacity indicates that which can withstand repeated charging and discharging.
  • the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer means that all the lithium ions in the non-aqueous electrolyte contained in the positive electrode active material layer are in the positive electrode active material.
  • the battery capacity based on the total amount of the positive electrode active material is calculated according to the following formula.
  • Battery capacity [mAh / cm 2 ] Positive electrode active material capacity [mAh / g] ⁇ Positive electrode active material basis weight [mg / cm 2 ] / 10 3
  • the positive electrode active material capacity [mAh / g] is the positive electrode active material (in the case where the positive electrode active material is a coated positive electrode active material coated with a coating layer containing a polymer compound), A mixture of non-aqueous electrolyte prepared by dissolving LiN (FSO 2 ) 2 at a ratio of 3 mol / L in a mixed solvent of (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) to form an aramid After applying to one side of a separator [manufactured by Japan Vilene Co., Ltd.], press for 10 seconds at a pressure of 10 MPa to prepare an electrode, and it is incorporated into the battery pack in a state facing the counter electrode (metal lithium
  • the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer can be uniquely derived from the thickness of the positive electrode active material layer, the porosity, and the electrolyte concentration of the non-aqueous electrolyte. It can be adjusted by combining them in a timely manner.
  • the calculation formula is as follows.
  • Battery capacity [mAh / cm 2 ] electrode void volume [cm 3 ] ⁇ electrolyte concentration of non-aqueous electrolyte [mol / L] based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer / 10 3 ⁇ capacity conversion constant [mAh / mol] / electrode area [cm 2 ] Capacity conversion constant [mAh / mol]: 26806 The capacity conversion constant represents the battery capacity per lithium ion.
  • Electrode void volume [cm 3 ] Porosity [volume%] ⁇ Electrode film thickness [ ⁇ m] / 10 4 ⁇ electrode area [cm 2 ]
  • the ratio of the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer (battery capacity ratio) relative to the battery capacity based on the total amount of the positive electrode active material is the type of the positive electrode active material, the positive electrode active material It can be controlled by the basis weight of the positive electrode active material in the material layer, the porosity of the positive electrode active material layer, the electrolyte concentration of the non-aqueous electrolyte, and the like.
  • the battery capacity based on the total amount of the positive electrode active material is increased and the battery capacity ratio is decreased.
  • increasing the electrolyte concentration of the non-aqueous electrolyte or increasing the porosity of the positive electrode active material layer increases the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer. As a result, the battery capacity ratio increases.
  • the positive electrode active material constituting the positive electrode for a lithium ion battery of the present invention those conventionally used as an active material for a positive electrode of a lithium ion battery can be suitably used.
  • a composite oxide of lithium and a transition metal a composite oxide having one kind of transition metal (such as LiCoO 2 , LiNiO 2 , LiAlMnO 4 , LiMnO 2, and LiMn 2 O 4 ), a transition metal element is used.
  • Two kinds of complex oxides for example, LiFeMnO 4 , LiNi 1-x Co x O 2 (where 0 ⁇ x ⁇ 1), LiMn 1-y Co y O 2 (where 0 ⁇ y ⁇ 1), LiNi 1 / 3 Co 1/3 Al 1/3 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2
  • lithium-containing Transition money Metal phosphates eg LiFePO 4 , LiCoPO 4 , LiMnPO 4 and LiNiPO 4
  • transition metal oxides eg MnO 2 and V 2 O 5
  • transition metal sulfides eg MoS 2 and TiS 2
  • high conductivity Molecule for example, polyaniline, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene and polyvinylcarbazole
  • the lithium-containing transition metal phosphate may be one in which a part of the transition metal site is substituted with another transition metal.
  • the volume average particle diameter of the positive electrode active material is preferably from 0.01 to 100 ⁇ m, more preferably from 0.1 to 35 ⁇ m, and further preferably from 2 to 30 ⁇ m, from the viewpoint of the electric characteristics of the battery.
  • the volume average particle diameter of the positive electrode active material means a particle diameter (Dv50) at an integrated value of 50% in the particle size distribution obtained by the microtrack method (laser diffraction / scattering method).
  • the microtrack method is a method for obtaining a particle size distribution using scattered light obtained by irradiating particles with laser light.
  • the Nikkiso Co., Ltd. microtrack etc. can be used for the measurement of a volume average particle diameter.
  • the positive electrode active material layer includes a positive electrode active material and voids.
  • the positive electrode active material layer includes voids, and a sufficient amount of lithium ions can be disposed around the positive electrode active material by filling the voids with a non-aqueous electrolyte containing lithium ions.
  • the volume of voids in the positive electrode active material layer is such that the battery capacity ratio based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer is 3.5 to 3.5% of the battery capacity based on the total amount of positive electrode active material.
  • the total volume of voids is preferably 35 to 60% by volume, more preferably 35 to 50% by volume of the total volume of the positive electrode active material layer as long as it is 15%.
  • the void refers to a void that the positive electrode active material layer has in a state where the positive electrode is not impregnated with the non-aqueous electrolyte.
  • the porosity can be obtained by image analysis of the cross section of the positive electrode active material layer by X-ray computed tomography (CT) or the like.
  • the measurement is performed by the following method.
  • the porosity is the total volume value of each component obtained by dividing the weight of each solid component (excluding electrolyte) constituting the positive electrode active material layer having a constant volume by the true density of each component.
  • the value obtained by subtracting from the volume of can be calculated by further dividing by the volume of the positive electrode active material layer.
  • the weight and true density of each solid component can be determined by solid-liquid separation of a cleaning solution obtained by cleaning the positive electrode with a non-aqueous solvent, and removing the non-aqueous solvent.
  • the solid component is not separated into a component that dissolves in a non-aqueous solvent and a component that does not dissolve, and as a mixture of solid components, the weight is divided by the true density to obtain the volume of the entire solid component, You may replace with the method of measuring a weight and a true density for every component.
  • the thickness of the positive electrode active material layer (hereinafter also simply referred to as film thickness) is not particularly limited, but is preferably 100 ⁇ m or more and 900 ⁇ m or less, and preferably 150 ⁇ m or more and 600 ⁇ m from the viewpoint of achieving both energy density and input / output characteristics. Or less, more preferably 200 ⁇ m or more and 400 ⁇ m or less.
  • the amount of the non-aqueous electrolyte that the positive electrode active material layer can hold per unit area is not particularly limited, but is preferably 6 to 120 ⁇ L / cm 2 .
  • the reference surface per unit area is a surface parallel to the surface of the positive electrode current collector.
  • the amount of the non-aqueous electrolyte that the positive electrode active material layer can hold per unit area is 6 ⁇ L / cm 2 or more, the total amount of lithium ions present around the positive electrode active material is sufficiently obtained, and the rate characteristics are excellent.
  • the amount of the non-aqueous electrolyte solution that can be held per unit area can be calculated from the porosity and film thickness of the positive electrode active material layer.
  • the positive electrode current collector is not particularly limited, but is copper, aluminum, titanium, stainless steel, nickel, calcined carbon, a conductive polymer (polymer having an electron conductive skeleton) or a nonconductive polymer material as a resin.
  • a conductive polymer polymer having an electron conductive skeleton
  • a nonconductive polymer material as a resin.
  • examples thereof include a material to which a conductive material is added if necessary, and a foil containing a conductive material such as conductive glass.
  • covered by the metal surface, or a carbon covering aluminum foil may be sufficient.
  • the conductive material contained in the resin current collector is selected from conductive materials. Specifically, metals [nickel, aluminum, stainless steel (SUS), silver, copper, titanium, etc.], carbon [graphite and carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), etc. , And mixtures thereof, but are not limited thereto.
  • These conductive materials may be used alone or in combination of two or more.
  • an alloy or metal oxide of the above metal may be used. From the viewpoint of electrical stability, aluminum, stainless steel, carbon, silver, copper, titanium and a mixture thereof are preferable, silver, aluminum, stainless steel and carbon are more preferable, and carbon is more preferable.
  • a particulate ceramic material or a resin material may be coated with a conductive material (a metal material among the above-described conductive materials) by plating or the like.
  • the average particle diameter of the conductive material is not particularly limited, but is preferably from 0.01 to 10 ⁇ m, more preferably from 0.02 to 5 ⁇ m, from the viewpoint of the electric characteristics of the battery. More preferably, the thickness is 03 to 1 ⁇ m.
  • the “particle diameter of the conductive material” means the maximum distance among any two points on the contour line of the conductive material.
  • the value of “average particle size” is the average value of the particle size of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.
  • the shape (form) of the conductive material is not limited to the particle form, and may be a form other than the particle form, and in a form that is put into practical use as a so-called filler-based conductive resin composition such as carbon nanofiller and carbon nanotube. There may be.
  • the conductive material may be a conductive fiber having a fibrous shape.
  • conductive fibers include carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, conductive fibers obtained by uniformly dispersing highly conductive metal and graphite in synthetic fibers, and metals such as stainless steel.
  • examples thereof include fiberized metal fibers, conductive fibers in which the surface of organic fiber is coated with metal, and conductive fibers in which the surface of organic fiber is coated with a resin containing a conductive substance.
  • carbon fibers are preferable.
  • a polypropylene resin in which graphene is kneaded is also preferable.
  • the average fiber diameter is preferably 0.1 to 20 ⁇ m.
  • the resins contained in the resin current collector include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polycycloolefin (PCO), polyethylene terephthalate (PET), polyether nitrile (PEN), polytetra Fluoroethylene (PTFE), styrene butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVdF), epoxy resin, silicone resin or a mixture thereof Is mentioned.
  • PE polyethylene
  • PP polypropylene
  • PMP polymethylpentene
  • PCO polycycloolefin
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PTFE polytetra Fluoroethylene
  • SBR styrene butadiene rubber
  • PAN polyacrylonitrile
  • PMA polymethyl acrylate
  • PMMA polymethyl methacryl
  • polyethylene (PE), polypropylene (PP), polymethylpentene (PMP) and polycycloolefin (PCO) are preferable, and polyethylene (PE), polypropylene (PP) and polymethylpentene are more preferable. (PMP).
  • non-aqueous electrolyte a non-aqueous electrolyte containing an electrolyte and a non-aqueous solvent used in the production of a lithium ion battery can be used.
  • electrolyte those used in known electrolyte solutions can be used, and preferable examples include lithium salt electrolytes of inorganic acids such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 and LiClO 4 , A sulfonylimide-based electrolyte having fluorine atoms such as LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 and LiN (C 2 F 5 SO 2 ) 2, and a fluorine atom such as LiC (CF 3 SO 2 ) 3 are used. Examples thereof include a sulfonylmethide-based electrolyte.
  • a sulfonylimide-based electrolyte having a fluorine atom is preferable from the viewpoint of ion conductivity at a high concentration and a thermal decomposition temperature, and LiN (FSO 2 ) 2 is more preferable.
  • LiN (FSO 2 ) 2 may be used in combination with other electrolytes, but is more preferably used alone.
  • the electrolyte concentration of the non-aqueous electrolyte is not particularly limited, but is preferably 1 to 5 mol / L, and preferably 1.5 to 4 mol / L from the viewpoints of the handleability of the non-aqueous electrolyte and battery capacity. More preferably, it is 2 to 3 mol / L.
  • non-aqueous solvent those used in known non-aqueous electrolytes can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphate esters. , Nitrile compounds, amide compounds, sulfones and the like and mixtures thereof.
  • lactone compound examples include 5-membered rings (such as ⁇ -butyrolactone and ⁇ -valerolactone) and 6-membered lactone compounds (such as ⁇ -valerolactone).
  • cyclic carbonate examples include propylene carbonate, ethylene carbonate and butylene carbonate.
  • chain carbonate examples include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.
  • chain carboxylic acid ester examples include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate.
  • cyclic ether examples include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane and the like.
  • chain ether examples include dimethoxymethane and 1,2-dimethoxyethane.
  • phosphate esters include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, tri (trichloromethyl) phosphate, Tri (trifluoroethyl) phosphate, tri (triperfluoroethyl) phosphate, 2-ethoxy-1,3,2-dioxaphosphoran-2-one, 2-trifluoroethoxy-1,3,2- Examples include dioxaphospholan-2-one and 2-methoxyethoxy-1,3,2-dioxaphosphoran-2-one.
  • nitrile compounds include acetonitrile.
  • amide compound examples include N, N-dimethylformamide (hereinafter referred to as DMF).
  • sulfone include chain sulfones such as dimethyl sulfone and diethyl sulfone, and cyclic sulfones such as sulfolane.
  • the non-aqueous solvent may be used alone or in combination of two or more.
  • lactone compounds, cyclic carbonates, chain carbonates, and phosphates are preferable from the viewpoint of battery output and charge / discharge cycle characteristics, and preferably do not contain a nitrile compound. More preferred are a lactone compound, a cyclic carbonate and a chain carbonate, and particularly preferred is a mixture of a cyclic carbonate and a chain carbonate. Most preferred is a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) or a mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • the positive electrode active material layer may further contain a conductive material.
  • the conductive material include conductive fibers.
  • the positive electrode active material layer further includes conductive fibers
  • the conductive fibers can function to assist electronic conduction in the positive electrode active material layer, and the conductive fibers described above are the conductive materials described in the resin current collector. The same thing as a property fiber can be used.
  • the positive electrode active material layer further contains conductive fibers, it is preferable to use a coated positive electrode active material described later as the positive electrode active material.
  • the content of the conductive fibers contained in the positive electrode active material layer is preferably 25% by weight or less with respect to the total weight of the positive electrode active material layer.
  • a conductive agent having no fibrous form may be used.
  • a conductive agent having a particulate (for example, spherical) form can be used.
  • the shape of the particles is not particularly limited, and may be any shape such as powder, sphere, plate, column, indefinite shape, flake shape, and spindle shape.
  • the conductive agent having a particulate (for example, spherical) form the same conductive material as that described for the resin current collector can be used.
  • the positive electrode active material is preferably partially or entirely covered with a coating layer containing a polymer compound.
  • the positive electrode active material in which part or all of the surface is coated with a coating layer is also referred to as a coated positive electrode active material.
  • a coated positive electrode active material When the surface of the positive electrode active material is coated with the coating layer, the volume change of the positive electrode is relaxed, and the expansion of the positive electrode can be suppressed. Furthermore, the wettability of the positive electrode active material with respect to the nonaqueous solvent can be improved.
  • Examples of the polymer compound constituting the coating layer include a polymer compound having a liquid absorption rate of 10% or more when immersed in a non-aqueous electrolyte and a tensile elongation at break in a saturated liquid absorption state of 10% or more. preferable.
  • the liquid absorption rate when immersed in the non-aqueous electrolyte is obtained by the following equation by measuring the weight of the polymer compound before and after being immersed in the non-aqueous electrolyte.
  • Absorption rate (%) [(weight of polymer compound after immersion in non-aqueous electrolyte ⁇ weight of polymer compound before immersion in non-aqueous electrolyte) / weight of polymer compound before immersion in non-aqueous electrolyte] ⁇ 100
  • a nonaqueous electrolytic solution dissolved to a concentration of L is used.
  • the saturated liquid absorption state refers to a state in which the weight of the polymer compound does not increase even when immersed in the non-aqueous electrolyte.
  • non-aqueous electrolyte used when manufacturing a lithium ion battery is not limited to the said non-aqueous electrolyte, You may use another non-aqueous electrolyte.
  • the polymer compound sufficiently absorbs the non-aqueous electrolyte, and lithium ions can easily permeate the polymer compound. The movement of lithium ions between electrolytes is not hindered. If the liquid absorption rate is less than 10%, the non-aqueous electrolyte does not easily penetrate into the polymer compound, so that the lithium ion conductivity is lowered and the performance as a lithium ion battery may not be sufficiently exhibited.
  • the liquid absorption is more preferably 20% or more, and further preferably 30% or more.
  • a preferable upper limit of a liquid absorption rate it is 400%, and as a more preferable upper limit, it is 300%.
  • the tensile elongation at break in the saturated liquid absorption state is obtained by punching the polymer compound into a dumbbell shape and immersing in a non-aqueous electrolyte at 50 ° C. for 3 days in the same manner as the measurement of the liquid absorption rate described above to saturate the polymer compound.
  • As a liquid absorption state it can measure based on ASTM D683 (test piece shape Type II).
  • the tensile elongation at break is a value obtained by calculating the elongation until the test piece breaks in the tensile test according to the following formula.
  • Tensile elongation at break (%) [(length of specimen at break ⁇ length of specimen before test) / length of specimen before test] ⁇ 100 If the tensile elongation at break in the saturated liquid absorption state of the polymer compound is 10% or more, the polymer compound has appropriate flexibility, and therefore the coating layer is peeled off due to the volume change of the positive electrode active material during charge / discharge. It becomes easy to suppress this.
  • the tensile elongation at break is more preferably 20% or more, and further preferably 30% or more. Further, the preferable upper limit value of the tensile elongation at break is 400%, and the more preferable upper limit value is 300%.
  • the polymer compound constituting the coating layer examples include thermoplastic resins and thermosetting resins, such as vinyl resins, urethane resins, polyester resins, polyamide resins, epoxy resins, polyimide resins, silicone resins, phenol resins, Examples include melamine resins, urea resins, aniline resins, ionomer resins, polycarbonates, polysaccharides (such as sodium alginate), and mixtures thereof. Of these, vinyl resins are preferred.
  • the vinyl resin is a resin comprising a polymer (A1) having a vinyl monomer (a) as an essential constituent monomer.
  • the polymer (A1) is a monomer containing a vinyl monomer (a1) having a carboxyl group or an acid anhydride group as the vinyl monomer (a) and a vinyl monomer (a2) represented by the following general formula (1).
  • a polymer of the composition is preferred.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a straight chain or branched alkyl group having 4 to 36 carbon atoms.
  • vinyl resins those having a liquid absorption rate of 10% or more when immersed in a non-aqueous electrolyte and a tensile elongation at break in a saturated liquid absorption state of 10% or more are more preferable.
  • Examples of the vinyl monomer (a1) having a carboxyl group or an acid anhydride group include monocarboxylic acids having 3 to 15 carbon atoms such as (meth) acrylic acid (a11), crotonic acid and cinnamic acid; (anhydrous) maleic acid, fumaric acid Dicarboxylic acids having 4 to 24 carbon atoms such as acid, (anhydrous) itaconic acid, citraconic acid and mesaconic acid; polycarboxylic acids having 6 to 24 carbon atoms such as aconitic acid and the like having a valence of 3 to 4 or more. Is mentioned. Among these, (meth) acrylic acid (a11) is preferable, and methacrylic acid is more preferable. In addition, (meth) acrylic acid shows acrylic acid and / or methacrylic acid.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 1 is preferably a methyl group.
  • R 2 is preferably a linear or branched alkyl group having 4 to 12 carbon atoms or a branched alkyl group having 13 to 36 carbon atoms.
  • (A21) R 2 is a linear or branched alkyl group having 4 to 12 carbon atoms.
  • Examples of the linear alkyl group having 4 to 12 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group can be mentioned.
  • Examples of the branched alkyl group having 4 to 12 carbon atoms include 1-methylpropyl group (sec-butyl group), 2-methylpropyl group, 1,1-dimethylethyl group (tert-butyl group), 1-methylbutyl group, 1 , 1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group 1-methylhexyl group, 2-methylhexyl group, 2-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethy
  • R 2 is a branched alkyl group having 13 to 36 carbon atoms.
  • the branched alkyl group having 13 to 36 carbon atoms include a 1-alkylalkyl group [1-methyldodecyl group, 1-butyleicosyl group, 1-hexyloctadecyl group, 1-octylhexadecyl group, 1-decyltetradecyl group, 1-undecyltridecyl group, etc.], 2-alkylalkyl group [2-methyldodecyl group, 2-hexyloctadecyl group, 2- Octylhexadecyl group, 2-decyltetradecyl group, 2-undecyltridecyl group, 2-dodecylhexadecyl group, 2-tridecylpentadecyl group, 2-decyloctadecyl group, 2-te
  • the polymer (A1) preferably further contains an ester compound (a3) of a monovalent aliphatic alcohol having 1 to 3 carbon atoms and (meth) acrylic acid.
  • Examples of the monovalent aliphatic alcohol having 1 to 3 carbon atoms constituting the ester compound (a3) include methanol, ethanol, 1-propanol and 2-propanol.
  • the content of the ester compound (a3) is preferably 10 to 60% by weight, and preferably 15 to 55% by weight based on the total weight of the polymer (A1) from the viewpoint of suppressing volume change of the positive electrode active material. More preferred is 20 to 50% by weight.
  • the polymer (A1) may further contain an anionic monomer salt (a4) having a polymerizable unsaturated double bond and an anionic group.
  • Examples of the structure having a polymerizable unsaturated double bond include a vinyl group, an allyl group, a styryl group, and a (meth) acryloyl group.
  • anionic group examples include a sulfonic acid group and a carboxyl group.
  • An anionic monomer having a polymerizable unsaturated double bond and an anionic group is a compound obtained by a combination thereof, such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid and (meth) acrylic acid. It is done.
  • the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • Examples of the cation constituting the salt (a4) of the anionic monomer include lithium ion, sodium ion, potassium ion and ammonium ion.
  • the anionic monomer salt (a4) When the anionic monomer salt (a4) is contained, its content is preferably 0.1 to 15% by weight based on the total weight of the polymer compound from the viewpoint of internal resistance and the like. It is more preferably ⁇ 15% by weight, and further preferably 2-10% by weight.
  • the polymer (A1) preferably contains (meth) acrylic acid (a11) and an ester compound (a21), and more preferably contains an ester compound (a3).
  • an ester compound (a3) preferably contains an ester compound (a3).
  • methacrylic acid as (meth) acrylic acid (a11)
  • 2-ethylhexyl methacrylate as ester compound (a21)
  • methyl methacrylate as ester compound (a3)
  • methacrylic acid, 2-ethylhexyl methacrylate and Most preferred is a copolymer of methyl methacrylate.
  • the polymer compound includes (meth) acrylic acid (a11), the above vinyl monomer (a2), an ester compound (a3) of a monovalent aliphatic alcohol having 1 to 3 carbon atoms and (meth) acrylic acid, and if necessary.
  • a monomer composition comprising a salt (a4) of an anionic monomer having a polymerizable unsaturated double bond and an anionic group to be used is polymerized, and the vinyl monomer (a2) and the (meta ) Acrylic acid (a11) weight ratio [the vinyl monomer (a2) / (meth) acrylic acid (a11)] is preferably 10/90 to 90/10.
  • the weight ratio of the vinyl monomer (a2) and (meth) acrylic acid (a11) is 10/90 to 90/10, the polymer obtained by polymerizing this has good adhesion to the positive electrode active material and is peeled off. It becomes difficult to do.
  • the weight ratio is, for example, 20/80 to 85/15, preferably 30/70 to 85/15, and more preferably 40/60 to 70/30.
  • the monomer constituting the polymer (A1) includes a vinyl monomer (a1) having a carboxyl group or an acid anhydride group, a vinyl monomer (a2) represented by the above general formula (1), and a carbon number of 1
  • a vinyl monomer (a1) having a carboxyl group or an acid anhydride group a vinyl monomer (a2) represented by the above general formula (1)
  • a carbon number of 1 In addition to the ester compound (a3) of a monovalent aliphatic alcohol of 1 to 3 and (meth) acrylic acid and a salt of an anionic monomer having a polymerizable unsaturated double bond and an anionic group (a4)
  • the vinyl monomer (a1) having a carboxyl group or an acid anhydride group, the vinyl monomer (a2) represented by the general formula (1), and a carbon number of 1 to 3 may be copolymerized with the ester compound (a3) of monovalent aliphatic alcohol 3 and (meth) acrylic acid, and may contain a radical polymeriz
  • the radical polymerizable monomer (a5) is preferably a monomer not containing active hydrogen, and the following monomers (a51) to (a58) can be used.
  • the monool (i) linear aliphatic monool (tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol Etc.), (ii) alicyclic monools (cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, cyclooctyl alcohol etc.), (iii) araliphatic monools (benzyl alcohol etc.) and mixtures of two or more thereof Can be mentioned.
  • (A52) Poly (n 2 to 30) oxyalkylene (carbon number 2 to 4) alkyl (carbon number 1 to 18) ether (meth) acrylate [methanol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct (meta ) Propylene oxide of acrylate, methanol (hereinafter abbreviated as PO), 10 mol adduct (meth) acrylate, etc.]
  • Vinyl hydrocarbons (a54-1) Aliphatic vinyl hydrocarbons Olefin having 2 to 18 or more carbon atoms (ethylene, propylene, Butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.), diene having 4 to 10 or more carbon atoms (butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7- Octadiene etc.) (a54-2) Alicyclic vinyl hydrocarbon Cyclic unsaturated compounds having 4 to 18 or more carbon atoms, such as cycloalkene (eg cyclohexene), (di) cycloalkadiene [eg (di) cyclopentadiene], terpene (eg pinene and limonene), indene (a54-3 ) Aromatic vinyl hydrocarbon Aromatic unsaturated
  • the content of the ester compound (a3) and (meth) acrylic acid, the salt (a4) of the anionic monomer having a polymerizable unsaturated double bond and an anionic group, and the radical polymerizable monomer (a5) is , Based on the weight of the polymer (A1), (a1) is 0.1 to 80% by weight, (a2) is 0.1 to 99.9% by weight, (a3) is 0 to 60% by weight, (a4 ) Is preferably 0 to 15% by weight, and (a5) is preferably 0 to 99.8% by weight.
  • the content of the monomer is within the above range, the liquid absorptivity to the non-aqueous electrolyte is good.
  • the preferable lower limit of the number average molecular weight of the polymer (A1) is 3,000, more preferably 50,000, still more preferably 100,000, particularly preferably 200,000, and the preferable upper limit is 2,000,000. It is preferably 1,500,000, more preferably 1,000,000, and particularly preferably 800,000.
  • the number average molecular weight of the polymer (A1) can be determined by gel permeation chromatography (hereinafter abbreviated as GPC) measurement under the following conditions.
  • GPC gel permeation chromatography
  • Apparatus Alliance GPC V2000 (manufactured by Waters) Solvent: Orthodichlorobenzene Reference material: Polystyrene detector: RI Sample concentration: 3 mg / ml
  • Column stationary phase PLgel 10 ⁇ m, MIXED-B 2 in series (manufactured by Polymer Laboratories) Column temperature: 135 ° C.
  • the polymer (A1) is a known polymerization initiator ⁇ azo initiator [2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2, 2′-azobis (2,4-dimethylvaleronitrile, etc.)], peroxide-based initiators (benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, etc.), etc. ⁇ (Bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
  • the amount of the polymerization initiator used is preferably from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, based on the total weight of the monomers, from the viewpoint of adjusting the number average molecular weight within a preferable range. More preferred is 0.1 to 1.5% by weight.
  • the polymerization temperature and polymerization time are adjusted according to the type of polymerization initiator, etc., but the polymerization temperature is preferably -5 to 150 ° C. (more preferably 30 to 120 ° C.), and the reaction time is preferably 0. 1 to 50 hours (more preferably 2 to 24 hours).
  • Examples of the solvent used in the solution polymerization include esters (having 2 to 8 carbon atoms such as ethyl acetate and butyl acetate), alcohols (having 1 to 8 carbon atoms such as methanol, ethanol and octanol), hydrocarbons (having carbon atoms).
  • the amount used is preferably 5 to 900% by weight, more preferably 10 to 400% by weight, based on the total weight of the monomers. More preferably, it is 30 to 300% by weight, and the monomer concentration is 10 to 9 Preferably wt%, more preferably 20 to 90 wt%, more preferably 30 to 80 wt%.
  • Examples of the dispersion medium in emulsion polymerization and suspension polymerization include water, alcohol (for example, ethanol), ester (for example, ethyl propionate), light naphtha and the like, and examples of the emulsifier include higher fatty acid (carbon number 10 to 24) metal salt.
  • alcohol for example, ethanol
  • ester for example, ethyl propionate
  • emulsifier include higher fatty acid (carbon number 10 to 24) metal salt.
  • sulfate metal salt for example, sodium lauryl sulfate
  • ethoxylated tetramethyldecynediol sodium sulfoethyl methacrylate, dimethylaminomethyl methacrylate, etc.
  • the monomer concentration of the solution or dispersion is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, more preferably 30 to 80% by weight.
  • the amount of the polymerization initiator used in the solution or dispersion is The content is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total weight of the above.
  • chain transfer agents such as mercapto compounds (such as dodecyl mercaptan and n-butyl mercaptan) and / or halogenated hydrocarbons (such as carbon tetrachloride, carbon tetrabromide and benzyl chloride) can be used.
  • mercapto compounds such as dodecyl mercaptan and n-butyl mercaptan
  • halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and benzyl chloride
  • the polymer (A1) contained in the vinyl resin is a crosslinking agent (A ′) having a reactive functional group that reacts the polymer (A1) with a carboxyl group ⁇ preferably a polyepoxy compound (a′1) [polyglycidyl ether].
  • Examples of the method of crosslinking the polymer (A1) using the crosslinking agent (A ′) include a method of crosslinking after coating the positive electrode active material with the polymer (A1). Specifically, a positive electrode active material and a polymer solution (A1) -containing resin solution are mixed and removed to produce a coated positive electrode active material in which the positive electrode active material is coated with the polymer (A1). The solution containing the agent (A ′) is mixed with the coated positive electrode active material and heated to cause solvent removal and a crosslinking reaction, and the polymer (A1) is crosslinked by the crosslinking agent (A ′). There is a method of causing a reaction to be a molecular compound on the surface of the positive electrode active material.
  • heating temperature is adjusted according to the kind of crosslinking agent, when using a polyepoxy compound (a'1) as a crosslinking agent, it is preferable that it is 70 degreeC or more, and when using a polyol compound (a'2) Is preferably 120 ° C. or higher.
  • the coating layer may further contain a conductive agent, and as the conductive agent that can be contained in the coating layer, the same conductive material as that contained in the resin current collector can be suitably used. The same applies to preferred forms, average particle diameters, and the like.
  • the ratio of the total weight of the polymer compound and the conductive agent contained in the coating layer is not particularly limited, but is preferably 0 to 25% by weight with respect to the weight of the positive electrode active material.
  • the ratio of the weight of the polymer compound to the weight of the positive electrode active material is not particularly limited, but is preferably 0.1 to 11% by weight.
  • the ratio of the weight of the conductive agent to the weight of the positive electrode active material is not particularly limited, but is preferably 0 to 14% by weight.
  • the coated positive electrode active material can be produced, for example, by mixing a polymer compound and a positive electrode active material.
  • the coating layer contains a conductive agent, it may be produced, for example, by mixing a polymer compound, a conductive agent, and a positive electrode active material.
  • a coating material was prepared by mixing a polymer compound and a conductive agent. Then, you may manufacture by mixing this coating
  • at least a part of the surface of the positive electrode active material is coated with the coating layer containing the polymer compound.
  • positive electrode active material and the polymer compound those described for the coated positive electrode active material can be preferably used.
  • the coated positive electrode active material is prepared by, for example, dropping and mixing a polymer solution containing a polymer compound over a period of 1 to 90 minutes in a state where the positive electrode active material is put in a universal mixer and stirred at 300 to 1000 rpm. Stir further. Further, if necessary, a conductive agent is mixed, and then, if necessary, stirring is continued for 10 minutes to 1 hour. After reducing the pressure to 0.007 to 0.04 MPa while stirring, the stirring and the degree of vacuum are maintained. It can be obtained by raising the temperature to 50 to 200 ° C. and holding for 10 minutes to 10 hours, preferably 1 to 10 hours. Thereafter, the coated positive electrode active material obtained as a powder may be classified.
  • Examples of the method for producing a positive electrode for a lithium ion battery according to the present invention include, for example, a positive electrode active material and a conductive agent to be used if necessary, based on the weight of a nonaqueous electrolyte or a nonaqueous solvent of the nonaqueous electrolyte.
  • a coating device such as a bar coater
  • the dispersion liquid is dried as necessary to obtain a nonaqueous electrolyte or a nonaqueous electrolyte solution.
  • a method of pressing the positive electrode active material layer obtained by removing the solvent or the like with a press if necessary and impregnating the obtained positive electrode active material layer with a predetermined amount of a non-aqueous electrolyte solution can be mentioned.
  • the positive electrode active material layer obtained from the dispersion does not need to be formed directly on the positive electrode current collector, for example, a positive electrode active material layer obtained by applying the dispersion on the surface of an aramid separator or the like, You may arrange
  • the drying performed as necessary after applying the dispersion liquid can be performed using a known dryer such as a forward air dryer, and the drying temperature is determined by the dispersion medium (non-aqueous electrolyte or It can be adjusted according to the type of nonaqueous solvent of the nonaqueous electrolytic solution.
  • a binder such as polyvinylidene fluoride (PVdF) contained in a known positive electrode for a lithium ion battery may be added to the dispersion, but the positive electrode active material is the above-described coated positive electrode active material. It is preferable not to add a binder.
  • the content of the binder is preferably 1% by weight or less, more preferably 0.5% by weight or less, with respect to 100% by weight of the total solid content contained in the positive electrode active material layer.
  • the amount is preferably 0.2% by weight or less, particularly preferably 0.1% by weight or less, and most preferably 0% by weight.
  • the binder is a polymer material added to bind the positive electrode active material particles and other members and maintain the structure of the positive electrode active material layer, and is a polymer compound for the coating layer included in the coating layer. Not included.
  • the binder is an insulating material that does not cause a side reaction (oxidation-reduction reaction) during charge and discharge, and generally satisfies the following three points: (1) A slurry used for the production of an active material layer is stable. Maintaining the state (having a dispersing action and a thickening action); (2) Electrode active particles, conductive assistants, etc. are adhered to each other, the mechanical strength as an electrode is maintained, and the particles are electrically Keeping contact; (3) Has adhesion (binding force) to the current collector.
  • the amount of addition is determined from the point that the active material layer can be molded while a sufficient amount of voids are formed in the positive electrode active material layer. It is preferably 0.1 to 20% by weight based on the minute weight.
  • binder examples include starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, styrene-butadiene rubber, polyethylene, and polypropylene.
  • the pressure at which the dried slurry is pressed is not particularly limited. However, if the pressure is too high, a sufficient amount of voids cannot be formed in the positive electrode active material layer. Since it is not observed, it is preferable to press at 1 to 200 MPa.
  • the preferred form of the positive electrode current collector is as described above.
  • the dispersion medium is a non-aqueous electrolyte or a non-aqueous solvent of a non-aqueous electrolyte, and when the applied dispersion is dried, the positive electrode active material layer obtained after drying
  • the weight of the non-aqueous electrolyte obtained by impregnating the non-aqueous electrolyte into the positive electrode active material layer is adjusted according to the void amount of the positive electrode active material layer and the electrolyte concentration of the non-aqueous electrolyte. be able to.
  • the impregnation of the positive electrode active material layer with the non-aqueous electrolyte solution can be performed by a method of dropping and impregnating the non-aqueous electrolyte solution onto the surface of the positive electrode active material layer formed by the above method using a dropper or the like. .
  • the lithium ion battery of the present invention is a battery using the above positive electrode for a lithium ion battery, and is combined with an electrode serving as a counter electrode of the above positive electrode for a lithium ion battery and accommodated in a cell container together with a separator. It can be manufactured by a method of injecting and sealing the cell container.
  • the negative electrode active material layer containing the negative electrode active material is formed on the other surface of the positive electrode current collector. It is also possible to produce a bipolar electrode by laminating the bipolar electrode with a separator and storing it in a cell container, injecting a non-aqueous electrolyte, and sealing the cell container.
  • separator examples include a microporous film made of polyethylene or polypropylene, a laminated film of a porous polyethylene film and porous polypropylene, a nonwoven fabric containing synthetic fibers (such as polyester fibers and aramid fibers) or glass fibers, and silica on the surface thereof.
  • synthetic fibers such as polyester fibers and aramid fibers
  • glass fibers such as glass fibers, and silica on the surface thereof.
  • separators for lithium ion batteries such as those to which ceramic fine particles such as alumina and titania are attached, may be mentioned.
  • non-aqueous electrolyte those described in the positive electrode for lithium ion batteries of the present invention can be suitably used.
  • the electrode (negative electrode) serving as a counter electrode of the positive electrode for a lithium ion battery a negative electrode used for a known lithium ion battery can be used.
  • the lithium ion battery of the present invention is characterized by using the positive electrode for a lithium ion battery of the present invention. Since the lithium ion battery of the present invention uses the positive electrode for a lithium ion battery of the present invention, rapid discharge is possible and the energy density is high.
  • ⁇ Production Example 2 Production of coated positive electrode active material particles> 100 parts of positive electrode active material powder (LiNi 0.8 Co 0.15 Al 0.05 O 2 powder, volume average particle diameter 4 ⁇ m) was put into a universal mixer high speed mixer FS25 [manufactured by Earth Technica Co., Ltd.], room temperature, 720 rpm In the state stirred in step 6.1, 6.1 parts of the coating polymer compound solution obtained in Production Example 1 was added dropwise over 2 minutes, and the mixture was further stirred for 5 minutes.
  • positive electrode active material powder LiNi 0.8 Co 0.15 Al 0.05 O 2 powder, volume average particle diameter 4 ⁇ m
  • acetylene black [DENKA BLACK (registered trademark) manufactured by Denka Co., Ltd.], which is a conductive agent, was added in 2 minutes while stirring, and stirring was continued for 30 minutes. Thereafter, the pressure was reduced to 0.01 MPa while maintaining the stirring, and then the temperature was raised to 140 ° C. while maintaining the stirring and the degree of vacuum, and the volatile matter was distilled off by maintaining the stirring, the degree of vacuum and the temperature for 8 hours. . The obtained powder was classified with a sieve having an opening of 212 ⁇ m to obtain coated positive electrode active material particles.
  • Example 1 [Preparation of positive electrode active material slurry for lithium ion battery] 20 parts of non-aqueous electrolyte prepared by dissolving LiN (FSO 2 ) 2 at a rate of 3 mol / L in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) and carbon fiber [ Osaka Gas Chemical Co., Ltd. Donakabo Milled S-243: average fiber length 500 ⁇ m, average fiber diameter 13 ⁇ m: electrical conductivity 200 mS / cm 2 parts and planetary agitation type mixing kneader ⁇ Awatori Kentaro [Sinky Co., Ltd.
  • the obtained positive electrode active material slurry was applied to one side of an aramid separator [manufactured by Japan Vilene Co., Ltd.] and pressed at a pressure of 10 MPa for about 10 seconds.
  • a positive electrode active material layer (3 cm ⁇ 3 cm) having a thickness of 230 ⁇ m was formed on the aramid separator. ) was fixed.
  • the basis weight (also referred to as basis weight) of the positive electrode active material was determined from the weight change of the aramid separator before and after forming the positive electrode active material layer, and found to be 52 mg / cm 2 .
  • an X-ray CT image is obtained as a cross-sectional image in two directions: a thickness direction of the aramid separator and a direction perpendicular thereto. Thereafter, for the 50 ⁇ m ⁇ 50 ⁇ m region extracted at 10 random locations in the cross-sectional images in each direction, the area occupied by the voids in the entire region was determined, and the average value thereof was taken as the porosity.
  • a carbon coated aluminum foil (3 cm ⁇ 3 cm, thickness 50 ⁇ m) with a terminal (5 mm ⁇ 3 cm) and a separator [manufactured by Celgard, Celgard (registered trademark) 3501, PP] (5 cm ⁇ 5 cm) and a terminal (5 mm ⁇ 3 cm) copper foil (3 cm ⁇ 3 cm, thickness 50 ⁇ m) is laminated in the same direction with two terminals coming out in the same direction, and two commercially available heat-sealing aluminum laminate films (8 cm ⁇ 8 cm) The one side where the terminal protrudes was heat-sealed to produce a laminate cell for positive electrode evaluation.
  • an aramid separator (3 cm ⁇ 3 cm) having a positive electrode active material layer fixed between the carbon-coated aluminum foil and the separator is inserted so that the positive electrode active material layer and the carbon-coated aluminum foil are in contact with each other, and an electrode (3 cm ⁇ 3 cm positive electrode)
  • a positive electrode for a lithium ion battery according to Example 1 was prepared by injecting 70 ⁇ L of a non-aqueous electrolyte into the active material layer) and allowing the electrode to absorb the non-aqueous electrolyte. Next, 70 ⁇ L of nonaqueous electrolyte was injected onto the separator.
  • a lithium foil was inserted between the separator and the copper foil, and two sides orthogonal to the one side heat-sealed first were heat sealed. Thereafter, 70 ⁇ L of nonaqueous electrolyte was injected from the opening, and the laminate was sealed by heat-sealing the opening while evacuating the inside of the cell using a vacuum sealer to obtain a lithium ion battery 1 for positive electrode evaluation. .
  • the battery capacity based on the total amount of lithium ions in the non-aqueous electrolyte present in the positive electrode active material layer is compared with the battery capacity based on the total amount of the positive electrode active material.
  • the ratio hereinafter also referred to as battery capacity ratio
  • Example 2 A lithium ion battery positive electrode and a positive electrode evaluation lithium ion battery 2 according to Example 2 were prepared in the same procedure as in Example 1, except that the electrolyte concentration of the non-aqueous electrolyte was changed from 3 mol / L to 2 mol / L. .
  • the porosity of the positive electrode active material layer was the same as in Example 1.
  • the battery capacity ratio was 6.3%.
  • Example 3 Except for changing the electrolyte concentration of the non-aqueous electrolyte from 3 mol / L to 1.2 mol / L, the lithium ion battery positive electrode and the positive electrode evaluation lithium ion battery 3 according to Example 3 were prepared in the same procedure as in Example 1. Produced. The porosity of the positive electrode active material layer was the same as in Example 1. The battery capacity ratio was 3.8%.
  • Example 4 The positive electrode active material slurry was changed so that the basis weight of the positive electrode active material was changed from 52 mg / cm 2 to 80 mg / cm 2 , the film thickness of the positive electrode active material layer was 320 ⁇ m, and the porosity was 46% by volume.
  • the lithium ion battery positive electrode and the positive electrode evaluation lithium ion battery 4 according to Example 4 were prepared in the same procedure as in Example 2 except that the press condition after coating on the aramid separator was changed to about 10 seconds at 20 MPa. Produced.
  • the film thickness of the positive electrode active material layer was 320 ⁇ m, and the porosity was 46% by volume.
  • the battery capacity ratio was 5.1%.
  • Example 5 A lithium ion battery positive electrode and a positive electrode evaluation lithium ion battery 5 according to Example 5 were prepared in the same procedure as in Example 4 except that the electrolyte concentration of the non-aqueous electrolyte was changed from 2 mol / L to 5 mol / L. .
  • the porosity of the positive electrode active material layer was the same as in Example 4.
  • the battery capacity ratio was 12.7%.
  • Example 6 The electrolyte of the non-aqueous electrolyte is changed from LiN (FSO 2 ) 2 to LiPF 6 and the positive electrode active material slurry is placed on the aramid separator so that the film thickness of the positive electrode active material layer is 390 ⁇ m and the porosity is 55% by volume.
  • a positive electrode for a lithium ion battery and a positive electrode evaluation lithium ion battery 6 according to Example 6 were produced in the same procedure as in Example 4 except that the press condition after coating was changed to about 10 seconds at 8 MPa.
  • the film thickness of the positive electrode active material was 390 ⁇ m, and the porosity was 55% by volume.
  • the battery capacity ratio was 7.4%.
  • the mixture was changed to a mixture, and the press condition after applying the positive electrode active material slurry on the aramid separator was changed to about 10 seconds at 40 MPa so that the film thickness of the positive electrode active material was 280 ⁇ m and the porosity was 38% by volume.
  • the basis weight of the positive electrode active material was 80 mg / cm 2 , the film thickness of the positive electrode active material layer was 280 ⁇ m, and the porosity was 38% by volume.
  • the battery capacity ratio was 5.6%.
  • a lithium ion battery positive electrode for positive electrode evaluation and a lithium ion battery 8 for positive electrode evaluation according to Example 8 were prepared in the same manner as in Example 1 except that the press condition after application on the aramid separator was changed to about 10 seconds at 8 MPa. Produced.
  • the film thickness of the positive electrode active material layer was 770 ⁇ m, and the porosity was 55% by volume.
  • the battery capacity ratio was 11.0%.
  • Example 2 In Example 1, the electrolyte concentration of the non-aqueous electrolyte was changed from 3 mol / L to 5.5 mol / L, but the electrolyte salt was precipitated in the electrolyte, and a non-aqueous electrolyte that could be used for a battery could not be created. The battery was not manufactured. Note that the battery capacity ratio is 17.3% when it is assumed that the battery is manufactured in the same manner as in Example 1 using the non-aqueous electrolyte having an electrolyte concentration of 5.5 mol / L.
  • the coated positive electrode active material particles produced in Production Example 2 are dissolved in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) at a rate of 3 mol / L of LiN (FSO 2 ) 2.
  • the slurry was mixed with the non-aqueous electrolyte prepared in this way and applied to one side of an aramid separator [manufactured by Japan Vilene Co., Ltd.], then pressed for 10 seconds at a pressure of 10 MPa to create an electrode, which was incorporated into the battery pack.
  • the discharge capacity when discharged from 2 V to 2.5 V was measured with a charge / discharge measuring device “Battery Analyzer 1470 type” (manufactured by Toyo Corporation), and the discharge capacity of the positive electrode active material (4.2 V ⁇ 2.5 V discharge) Capacity). The result was 192 mAh / g.
  • the positive electrode evaluation lithium ion batteries 1 to 8 and the positive electrode comparative evaluation lithium ion batteries 1 and 3 to 4 were charged to 4.2 V at a current of 0.05 C, respectively,
  • the capacity (1.0 C discharge capacity) when discharged to 2.5 V with current was measured.
  • the ratio [%] of the 1.0 C discharge capacity to the battery capacity based on the total amount of the positive electrode active material was determined by [(1.0 C discharge capacity) / (battery capacity based on the total amount of positive electrode active material) ⁇ 100], and the results are shown. 1 and 2. It means that the larger the 1.0C discharge capacity with respect to the battery capacity, the better and the faster discharge is possible.
  • Tables 1 and 2 show that the lithium ion battery using the positive electrode for a lithium ion battery of the present invention can increase the energy density and is excellent in rapid discharge characteristics.
  • the ratio of the 1.0 C discharge capacity to the battery capacity of Examples 5 to 8 is lower than that of Comparative Example 1, which is considered to be affected by the film thickness of the positive electrode active material layer. It is done.
  • the lithium ion battery using the positive electrode for the lithium ion battery of the present invention has excellent rapid charge / discharge characteristics. Conceivable.
  • the positive electrode for lithium ion batteries of the present invention is particularly useful as a positive electrode for bipolar secondary batteries and lithium ion secondary batteries used for mobile phones, personal computers, hybrid vehicles and electric vehicles.

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Abstract

Le problème décrit par la présente invention est de fournir une électrode positive pour une batterie au lithium-ion qui a une densité d'énergie élevée et qui peut être rapidement déchargée. La solution selon l'invention porte sur une électrode positive pour une batterie au lithium-ion, l'électrode positive comprenant : un collecteur d'électrode positive; une couche de matériau actif d'électrode positive formée sur la surface du collecteur d'électrode positive; et une solution d'électrolyte non aqueux contenant un solvant non aqueux et un électrolyte comprenant des ions lithium. L'électrode positive pour une batterie au lithium-ion est caractérisée en ce que la couche de matériau actif d'électrode positive contient un matériau actif d'électrode positive et des vides, les vides étant remplis avec la solution d'électrolyte non aqueux, et le rapport de la capacité de batterie sur la base de la quantité totale d'ions lithium dans la solution d'électrolyte non aqueux présente dans la couche de matériau actif d'électrode positive à la capacité de batterie sur la base de la quantité totale du matériau actif d'électrode positive est de 3,5 à 15 %.
PCT/JP2017/040164 2016-11-07 2017-11-07 Électrode positive pour batterie au lithium-ion, et batterie au lithium-ion WO2018084320A1 (fr)

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MYPI2019002468A MY176071A (en) 2016-11-07 2017-11-07 Positive electrode for lithium ion battery and lithium ion battery
EP17867325.7A EP3537514B1 (fr) 2016-11-07 2017-11-07 Électrode positive pour batterie au lithium-ion et batterie au lithium-ion
US16/346,337 US11024835B2 (en) 2016-11-07 2017-11-07 Positive electrode for lithium ion battery and lithium ion battery
CN201780068937.4A CN110249456B (zh) 2016-11-07 2017-11-07 锂离子电池用正极和锂离子电池

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CN113748538A (zh) * 2019-03-28 2021-12-03 Ａｐｂ株式会社 锂离子电池用部件的制造方法

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